EP3819962A1 - Couche d'électrode négative pour batterie secondaire tout solide, batterie secondaire toutsolide la comprenant et son procédé de préparation - Google Patents

Couche d'électrode négative pour batterie secondaire tout solide, batterie secondaire toutsolide la comprenant et son procédé de préparation Download PDF

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EP3819962A1
EP3819962A1 EP20206270.9A EP20206270A EP3819962A1 EP 3819962 A1 EP3819962 A1 EP 3819962A1 EP 20206270 A EP20206270 A EP 20206270A EP 3819962 A1 EP3819962 A1 EP 3819962A1
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Prior art keywords
layer
lithium
active material
negative
electrode layer
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German (de)
English (en)
Inventor
Minsuk Lee
Younggyoon RYU
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Samsung SDI Co Ltd
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Samsung SDI Co Ltd
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Publication of EP3819962A1 publication Critical patent/EP3819962A1/fr
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    • H—ELECTRICITY
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    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/134—Electrodes based on metals, Si or alloys
    • H—ELECTRICITY
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    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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    • H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
    • H01M10/0561—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of inorganic materials only
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    • H01M10/0585—Construction or manufacture of accumulators having only flat construction elements, i.e. flat positive electrodes, flat negative electrodes and flat separators
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    • H01M4/136—Electrodes based on inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy
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    • H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
    • H01M4/381—Alkaline or alkaline earth metals elements
    • H01M4/382—Lithium
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    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/483—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides for non-aqueous cells
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    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
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    • H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
    • H01M2004/027—Negative electrodes
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    • H01M2300/0068—Solid electrolytes inorganic

Definitions

  • One or more embodiments of the present disclosure relate to negative electrode layers for all-solid secondary batteries, all-solid secondary batteries including the same, and preparation methods thereof.
  • An all-solid secondary battery includes a positive electrode layer, a solid electrolyte layer, and a negative electrode layer.
  • the solid electrolyte layer should have high ionic conductivity and low electronic conductivity.
  • a sulfide-based solid electrolyte, an oxide-based solid electrolyte, and/or the like may be used as a solid electrolyte layer in all-solid secondary batteries.
  • the sulfide-based solid electrolyte is activated by pressing under high-temperature and high-pressure conditions.
  • low temperature or low pressure may increase cell resistance, thereby deteriorating or reducing battery performance.
  • the lithium metal behaves like a gel under high-temperature and high-pressure conditions. Therefore, deformation of an electrode plate may occur during an early stage of the pressing process, causing short-circuits after the manufacture of cells or during charging.
  • One or more embodiments of the present disclosure include a novel negative electrode layer for all-solid secondary batteries.
  • One or more embodiments include an all-solid secondary battery having improved performance by including embodiments of the negative electrode layer described herein and a preparation method thereof.
  • a negative electrode layer for sulfide-based solid electrolyte-containing all-solid secondary batteries includes a negative current collector and a first negative active material layer on the negative current collector, wherein the first negative active material layer includes a lithium metal composite including a lithium metal and an inorganic negative active material.
  • the inorganic negative active material comprises lithium fluoride, lithium oxide, lithium carbonate, lithium hydroxide, or any combination thereof.
  • an amount of the lithium metal in the lithium metal composite is in a range of 70 parts by weight to 99 parts by weight based on 100 parts by weight of the lithium metal composite.
  • the negative electrode layer further comprises a thin film of a metal and/or a metalloid between the negative current collector and the first negative active material layer.
  • the thin film of the metal and/or the metalloid comprises gold (Au), silver (Ag), magnesium (Mg), zinc (Zn), silicon (Si), tin (Sn), platinum (Pt), palladium (Pd), aluminum (Al), bismuth (Bi), or any combination thereof, and a thickness of the thin film of the metal or the metalloid is in a range of 1 nm to 800 nm.
  • the negative electrode layer further comprises a second negative active material layer, wherein the second negative active material layer comprises a metal, a metalloid element, or any combination thereof, each alloyable with lithium, and the second negative active material layer comprises a metal layer comprising lithium and/or a lithium alloy.
  • an all-solid secondary battery includes: a positive electrode layer; a negative electrode layer; a solid electrolyte layer interposed between the positive electrode layer and the negative electrode layer and including a sulfide-based solid electrolyte, wherein the negative electrode layer is the above-described negative electrode layer.
  • a second negative active material layer is located on the first negative active material layer.
  • the all-solid secondary battery further comprises a carbon layer between the first negative active material layer and the sulfide-based solid electrolyte layer.
  • the sulfide-based solid electrolyte layer comprises at least one selected from Li 2 S-P 2 S 5 , Li 2 S-P 2 S 5 -LiX wherein X is a halogen atom, Li 2 S-P 2 S 5 -Li 2 O, Li 2 S-P 2 S 5 -Li 2 O-LiI, Li 2 S-SiS 2 , Li 2 S-SiS 2 -LiI, Li 2 S-SiS 2 -LiBr, Li 2 S-SiS 2 -LiCl, Li 2 S-SiS 2 -B 2 S 3 -LiI, Li 2 S-SiS 2 -P 2 S 5 -LiI, Li 2 S-B 2 S 3 , Li 2 S-P 2 S 5 -Z m S n wherein m and n are positive numbers and Z is Ge, Zn, or Ga, Li 2 S-GeS 2 , Li 2 S-SiS 2 -Z m
  • the sulfide-based solid electrolyte layer comprises an argyrodite-type solid electrolyte comprising at least one selected from Li 5 PS 5 Cl, Li 6 PS 5 Br, and Li 6 PS 5 I.
  • the argyrodite-type solid electrolyte has a density in a range of 1.5 g/cc to 2.0 g/cc.
  • a method of preparing an all-solid secondary battery includes: providing a negative electrode layer including a negative current collector and a first negative active material layer; providing a positive electrode layer; preparing a laminated structure by providing a solid electrolyte layer including a sulfide-based solid electrolyte between the negative electrode layer and the positive electrode layer; and pressing the laminated structure, wherein the first negative active material layer includes a lithium metal composite including a lithium metal and an inorganic negative active material.
  • the providing of the negative electrode layer comprises: plating lithium on the negative current collector to prepare a plated lithium layer; and pressing the plated lithium layer, thereby preparing the negative electrode layer comprising the negative current collector and the first negative active material layer comprising the lithium metal composite.
  • the method further comprises: forming a metal coating layer for lithium nucleation on the negative current collector before performing the plating of lithium on the negative current collector, and then performing the plating of lithium on the metal coating layer to prepare the negative electrode layer comprising the negative current collector, the metal coating layer for lithium nucleation, and the first negative active material layer comprising the lithium metal composite.
  • the plating of lithium is performed by using a lithium plate and a liquid electrolyte that includes a lithium salt and an organic solvent.
  • the organic solvent is a mixed solvent comprising a glyme-based solvent and a fluorinated ether-based solvent, and an amount of the fluorinated ether-based solvent is in a range of 10 vol% to 95 vol% based on a total volume of the mixed solvent.
  • the glyme-based solvent comprises at least one selected from ethyleneglycol, dimethyl ether (DME), diethyltetraethyleneglycol dimethyl ether (TEGDME), and diethyleneglycol dimethylether (DEGDME), and the fluorinated ether-based solvent comprises 1,1,2,2-tetrafluoroethyl-2,2,3,3-tetrafluoropropyl ether, 1,1,2,2,-tetrafluoroethyl-1H,1H,5H-octafluoropentyl ether, 1,1,2,2-tetrafluoroethyl-2,2,2-trifluoroethyl ether, or any mixture thereof.
  • DME dimethyl ether
  • TEGDME diethyltetraethyleneglycol dimethyl ether
  • DEGDME diethyleneglycol dimethylether
  • the fluorinated ether-based solvent comprises 1,1,2,2-tetrafluoroethyl-2,2,3,3-te
  • a negative electrode layer as set out in claim 1. Additional features are set out in claims 2 to 5.
  • an all-solid secondary battery layer as set out in claim 6. Additional features are set out in claims 7 to 10.
  • a negative electrode layer for all-solid secondary batteries, an all-solid secondary battery including the same, and a preparation method thereof will be exemplarily described herein in more detail with reference to the accompanying drawings.
  • the negative electrode layer includes a negative current collector and a first negative active material layer, wherein the first negative active material layer includes a lithium metal composite including a lithium metal and an inorganic negative active material.
  • the inorganic negative active material is a lithium fluoride, a lithium oxide, a lithium carbonate, a lithium hydroxide, or any combination thereof.
  • an amount of the lithium metal is in a range of 70 parts by weight to 99 parts by weight, for example, 80 parts by weight to 99 parts by weight, or, for example, 95 parts by weight to 98 parts by weight based on 100 parts by weight of the lithium metal composite.
  • the lithium metal composite has good elasticity and hardness.
  • the lithium metal When the lithium metal is used as a negative active material in an all-solid secondary battery including a sulfide-based solid electrolyte, the lithium metal may be liquefied due to a softness of the lithium metal, thereby causing deformation of an electrode plate under high-temperature and high-pressure conditions applied to a laminated structure of a negative electrode layer, an electrolyte layer, and a positive electrode.
  • a part of the lithium metal may penetrate into the sulfide-based solid electrolyte, thereby causing short-circuits during charging or a decrease in lifespan due to internal cracks and short-circuits.
  • the present inventors have conducted research to address the above-mentioned issues and found that lifespan of an all-solid secondary battery may be increased by introducing lithium into the negative electrode layer in the form of a lithium metal composite (LMC) having high elasticity and hardness as another Li reservoir as well as the positive electrode layer, thereby completing the manufacture of the all-solid secondary battery.
  • LMC lithium metal composite
  • the negative electrode layer for all-solid secondary batteries includes the LMC, liquefaction and short-circuits do not occur during a pressing process performed with a high pressure for preparing batteries.
  • the negative electrode layer according to an embodiment is electrochemically stable against a sulfide-based solid electrolyte and may increase discharge capacity because lithium loss caused by irreversible reaction during initial charging by locating an Li reservoir in the negative electrode layer. Also, lifespan of the batteries may further be increased by making up for lithium loss caused by side reactions during charging and discharging.
  • a thickness of the first negative active material layer is in a range of 1 ⁇ m to 20 ⁇ m, for example, 1 ⁇ m to 10 ⁇ m, for example, 2 ⁇ m to 8 ⁇ m, or, for example, 4 ⁇ m to 6 ⁇ m.
  • a thin film of a metal or a metalloid may further be included between the negative current collector and the first negative active material layer.
  • the metal or metalloid thin film may include gold (Au), silver (Ag), magnesium (Mg), zinc (Zn), silicon (Si), tin (Sn), platinum (Pt), palladium (Pd), aluminum (Al), bismuth (Bi), or any combination thereof, and a thickness of the metal or metalloid thin film may be in a range of 1 nm to 800 nm, or, for example, 10 nm to 30 nm.
  • the first negative active material layer may have a porous structure.
  • a length of a major axis of a pore may be in a range of 50 nm to 5 ⁇ m, for example, 100 nm to 3 ⁇ m, or, for example, 100 nm to 2 ⁇ m.
  • a length of a minor axis of the pore may be in a range of 10 nm to 1 ⁇ m, for example, 50 nm to 500 nm, or, for example, 50 nm to 250 nm.
  • a total pore area per unit area is less than 50%, for example, less than 30%, or, for example, in a range of 5% to 15%.
  • all-solid secondary batteries having high voltage, high capacity, and/or long lifespan characteristics may be manufactured.
  • the negative electrode layer according to an embodiment may further include a second negative active material layer.
  • the second negative active material layer may be formed on the first negative active material layer.
  • the second negative active material layer may include a metal or metalloid element or any combination thereof which is alloyable with lithium.
  • the second negative active material layer may include a metal layer including lithium and/or a lithium alloy.
  • the surface of the second negative active material layer may include lithium fluoride (LiF).
  • the second negative active material layer may be a lithium free region not including lithium metal and/or lithium alloy during an early stage and/or after discharging of an all-solid secondary battery.
  • the negative electrode layer Before charging, the negative electrode layer may have a structure including a negative current collector, a coating layer for lithium nucleation (a metal layer and/or a metalloid layer), and a first negative active material layer. After charging the negative electrode layer, the second negative active material layer may be formed on the first negative active material layer.
  • the second negative active material layer may be non-porous.
  • a carbon layer may further be included between the first negative active material layer and a sulfide-based solid electrolyte-containing solid electrolyte layer.
  • the carbon layer may be formed of, for example, carbon black, carbon fiber, graphite, carbon nanotube, or any combination thereof.
  • the carbon layer formed as described above lowers resistance between the first negative active material layer and the solid electrolyte layer and assists uniform (e.g., substantially uniform) nucleation during the early stage and lithium grows between the LMC and carbon of the carbon layer, thereby inhibiting or reducing the formation of lithium dendrites.
  • an all-solid secondary battery including the negative electrode layer further including the carbon layer may have more improved lifespan characteristics compared to an all-solid secondary battery including a negative electrode layer not including a carbon layer.
  • FIGS. 1A and 1B a method of preparing a negative electrode layer for all-solid secondary batteries according to an embodiment will be further described.
  • LMC lithium metal composite
  • a metal coating layer 25 for lithium nucleation is formed on the negative current collector 21.
  • the metal coating layer 25 for lithium nucleation may be omitted.
  • the metal coating layer 125 for lithium nucleation enables uniform (e.g., substantially uniform) Li nucleation during plating, thereby promoting lithium plating and assisting uniform (e.g., substantially uniform) plating.
  • the metal coating layer 25 for lithium nucleation may be formed using a metal such as, for example, zinc (Zn), gold (Au), and/or silver (Ag) to a thickness in a range of about 1 nm to 50 nm, for example, 5 nm to 20 nm by using a thermal evaporator, and/or the like.
  • lithium 26 is plated on the metal coating layer 25 for lithium nucleation.
  • a lithium plate is used as a lithium source.
  • the Li plating may be performed by electroplating, electroless plating, and/or galvanic plating.
  • the Li plating may be performed by galvanic plating.
  • the galvanic plating is performed using two electrodes, a bath containing an electrolytic solution including a lithium salt and an organic solvent, and a lithium plate as a lithium source. A galvanic current is supplied to respective terminals of the two electrodes, and then lithium may be plated on the negative current collector in a porous form.
  • a shape of lithium plated on the metal coating layer 25 for lithium nucleation by the lithium plating varies according to plating conditions.
  • lithium may be formed in the form of strings, moss, branches, spheres, and/or the like.
  • Li particles tend to grow perpendicularly (e.g., substantially perpendicularly) to the negative current collector 21.
  • Li 26 grows horizontally (e.g., is compressed horizontally or in a direction substantially parallel to the negative current collector 21) as shown in FIG. 1B .
  • a solid electrolyte interface (SEI) layer 13 is formed on the surface of each particle of the Li 26.
  • the SEI layer 27 is formed from degradation products of the electrolytic solution and a composition and a thickness of the SEI layer 27 may vary according to the composition of the electrolytic solution.
  • the composition and thickness of the SEI layer 27 may vary according to the composition of the electrolytic solution used during plating.
  • the SEI layer 27 may include, for example, LiF as a main component.
  • LiFSI lithium bis(fluorosulfonyl)imide
  • the SEI layer 27 may include lithium fluoride (LiF) as a main component.
  • Lithium fluoride (LiF) which is, for example, self-formed on the surface of Li during plating as a SEI layer, is dense and has a Young's modulus in a range of about 65 GPa and a hardness of 1.3 GPa, thereby having high elasticity, hardness, and/or ionic conductivity.
  • Li 26 is surrounded by the SEI layer 27 formed of LiF having high elasticity and/or hardness, a wide range of chemical stability with a voltage of 0 V to 6.5 V (vs. Li/Li + ) may be obtained.
  • the LMC layer has excellent stability against high pressure because the pure Li 26 is surrounded by the SEI layer 27 including LiF.
  • a thickness of the SEI layer 27 is, for example, less than 100 nm, for example, in a range of 1 nm to 80 nm, for example, 1 nm to 60 nm, for example, 1 nm to 50 nm, for example, 1 nm to 30 nm, or, for example, 1 nm to 20 nm.
  • a pressure is applied to a porous structure of lithium coated with the SEI layer 27 according to the above-described process.
  • the pressure is applied using a roll press.
  • the pressure may be, for example, 500 MPa or more, for example, 550 MPa or more, for example, in a range of 500 MPa to 700 MPa, or, for example, in a range of 550 MPa to 600 MPa. Because the porous structure of Li becomes thinner and smoother through this pressing process and the porous structure of Li is surrounded by the SEI layer, pure Li does not (or substantially does not) leak therefrom during the pressing process.
  • the porous structure of Li may be thinned to (e.g., compressed to) a thickness of about 20% of an initial thickness.
  • the LMC layer 28 is suitable as a negative active material of a sulfide-based all-solid secondary battery that utilizes (or requires) pressing with pressure in a range of 400 MPa to 550 MPa.
  • the LMC layer 28 has a thickness in a range of 5 ⁇ m to 50 ⁇ m before pressing and a thickness in a range of 1 ⁇ m to 10 ⁇ m, or, for example, 4 ⁇ m to 6 ⁇ m after pressing.
  • the LMC layer 28 has a surface roughness (Rmax) in a range of 150 nm to 300 nm. When a surface roughness of the LMC layer 28 is within the range above, occurrence of cracks and short-circuits may be prevented or reduced in advance in the solid electrolyte layer while pressing cells.
  • the LMC layer may include SEI products.
  • the LMC layer may include LiF, Li 2 O, Li 2 CO 3 , LiOH, or any combination thereof and LiF may account for about 80 wt% or higher of the LMC layer based on the total weight of the LMC layer (e.g., the LiF may be present in the LMC layer in an amount of 80 wt% or more based on the total weight of the LMC layer).
  • the electrolytic solution used during Li plating may include a lithium salt and an organic solvent.
  • the lithium salt may include, for example, at least one selected from LiPF 6 , LiBF 4 , LiCF 3 SO 3 , Li(CF 3 SO 2 ) 2 N, LiC 2 F 5 SO 3 , Li(FSO 2 ) 2 N(LiFSI), LiC 4 F 9 SO 3 , LiN(SO 2 CF 2 CF 3 ) 2 , and compounds represented by the following formulae.
  • a concentration of the lithium salt is in a range of 0.01 M to 5.0 M, for example, 0.05 M to 5.0 M, for example, 0.1 M to 5.0 M, or, for example, 0.1 M to 2.0 M.
  • concentration of the lithium salt is within any of the ranges above, a thin and uniform (e.g., substantially uniform) LMC layer to which a high voltage is applicable may be prepared (e.g., it may be suitable to apply a high voltage to the LMC layer).
  • a mixed solvent including a glyme-based solvent and a fluorinated ether-based solvent may be used.
  • the glyme-based solvent includes at least one selected from ethyleneglycol, dimethyl ether (DME), tetraethyleneglycol dimethyl ether (TEGDME), and diethylene glycol dimethyl ether (DEGDME).
  • fluorinated ether-based solvent examples include 1,1,2,2-tetrafluoroethyl-2,2,3,3-tetrafluoropropyl ether (Product Name: HFE-458), 1,1,2,2-tetrafluoroethyl-1H,1H,5H-octafluoropentyl ether (Product Name: HFE-6512), 1,1,2,2-tetrafluoroethyl-2,2,2-trifluoroethyl ether (Product Name: HFE-347), or any mixture thereof.
  • HFE-458 1,1,2,2-tetrafluoroethyl-2,2,3,3-tetrafluoropropyl ether
  • HFE-6512 1,1,2,2-tetrafluoroethyl-1H,1H,5H-octafluoropentyl ether
  • HFE-347 1,1,2,2-tetrafluoroethyl-2,2,2-trifluoroethyl ether
  • An amount of the fluorinated ether-based solvent may be in a range of 10 vol% to 95 vol%, for example, 20 vol% to 90 vol%, for example, 30 vol% to 85 vol%, or, for example, 50 vol% to 80 vol%.
  • the glyme-based solvent has the ability to dissolve a lithium salt such as LiFSI and the fluorinated ether-based solvent does not have (or substantially does not have) the ability to dissolve a lithium salt.
  • the fluorinated ether-based solvent is used for diluting and may make a locally high-concentration lithium salt electrolytic solution.
  • Li is uniformly (e.g., substantially uniformly) plated at a locally high concentration.
  • the lithium layer may be uniformly (e.g., substantially uniformly) formed in the form of a thin film but also it is possible to apply a high pressure thereto.
  • the pressing of the plated lithium layer is performed by roll-pressing the plated Li film at a temperature in a range of 5 °C to 90 °C at a pressure of 500 MPa or more.
  • the plated Li film formed on the negative current collector according to the above-described process is porous, and an electrodeposition density of lithium is 0.2 g/cm 3 or less, or, for example, in a range of 0.05 g/cm 3 to 0.15 g/cm 3 .
  • the plated Li film loses porosity (e.g., pore volume and/or pore number may be reduced) and becomes flat (e.g., substantially flat) and the SEI layer (LiF) and Li are compressed to improve electrical connection between Li particles, thereby forming a negative electrode layer 20 having a structure in which the metal coating layer 25 for lithium nucleation and the lithium metal composite layer 28 are sequentially stacked on the negative current collector 21.
  • porosity e.g., pore volume and/or pore number may be reduced
  • the SEI layer (LiF) and Li are compressed to improve electrical connection between Li particles, thereby forming a negative electrode layer 20 having a structure in which the metal coating layer 25 for lithium nucleation and the lithium metal composite layer 28 are sequentially stacked on the negative current collector 21.
  • the negative electrode layer 20 including the negative current collector 21 and the lithium metal composite layer (first negative active material layer) 28 including the lithium metal composite is prepared.
  • the metal coating layer 25 for lithium nucleation may further be formed between the negative current collector 21 and the first negative active material layer .
  • the LMC layer 28 has mechanical properties significantly different from those of Li metal.
  • the LMC layer has a Young's modulus in a range of 10 GPa to 25 GPa, or, for example, 12 GPa to 22 GPa. Young's moduli of existing lithium layers are in a range of 4 GPa to 7 GPa. Because the LMC layer according to an embodiment has a higher Young's modulus than those of existing lithium layers, thereby having excellent mechanical properties.
  • the term "Young's modulus” has the same meaning as the term "tensile modulus,” as used in the art.
  • the tensile modulus is measured by using a dynamic mechanical analysis system (e.g., model DMA800, available from TA Instruments), and a protective layer specimen is prepared in compliance with ASTM standard D412 (Type V specimens).
  • a tensile modulus of the protective layer is obtained by measuring strain change against stress at a rate of 5 mm/min at 25 °C with a relative humidity of about 30%. Based on a stress-strain curve obtained as described above, the tensile modulus is evaluated.
  • the Young's modulus of the protective layer according to an embodiment may be easily measured by isolating a protective layer of a battery.
  • the Young's modulus of an isolated protective layer may be measured, using the above-described method and device for measuring Young's modulus by one of ordinary skill in the art.
  • an all-solid secondary battery including: a positive electrode layer; a negative electrode layer according to an embodiment; and a solid electrolyte layer including a sulfide-based solid electrolyte interposed between the positive electrode layer and the negative electrode layer.
  • the all-solid secondary battery includes: a positive electrode layer; a negative electrode layer; and a solid electrolyte layer interposed between the positive electrode layer and the negative electrode layer, wherein the positive electrode layer includes a positive current collector and a positive active material layer formed on the positive current collector, and the negative electrode layer includes a negative current collector and a first negative active material layer located on the negative current collector and including a lithium metal composite.
  • the all-solid secondary battery 1 includes: a positive electrode layer 10; a negative electrode layer 20; and a solid electrolyte layer 30 interposed between the positive electrode layer 10 and the negative electrode layer 20, wherein the positive electrode 10 includes a positive current collector 11 and a positive active material layer 12 formed on the positive current collector 11, and the negative electrode layer 20 includes a negative current collector 21 and a first negative active material layer 22 located on the negative current collector 21 and including a lithium metal composite (e.g., an LMC layer).
  • a lithium metal composite e.g., an LMC layer
  • the positive current collector 11 may be formed of, for example, indium (In), copper (Cu), magnesium (Mg), stainless steel, titanium (Ti), iron (Fe), cobalt (Co), nickel (Ni), zinc (Zn), aluminum (Al), germanium (Ge), lithium (Li), or any alloy thereof in the form of a plate, foil, and/or the like.
  • the positive current collector 11 may be omitted.
  • Positive Electrode Layer Positive Active Material
  • the positive active material layer 12 include, for example, a positive active material and a solid electrolyte.
  • the solid electrolyte included in the positive electrode layer 10 is similar to or different from a solid electrolyte included in the solid electrolyte layer 30.
  • the solid electrolyte and the solid electrolyte layer 30 are further described elsewhere herein.
  • the positive active material may include any suitable positive active material capable of reversibly absorbing and desorbing lithium ions.
  • the positive active material may include a lithium transition metal oxide such as, for example, lithium cobalt oxide (LCO), lithium nickel oxide, lithium nickel cobalt oxide, lithium nickel cobalt aluminum oxide (NCA), lithium nickel cobalt manganese oxide (NCM), lithium manganate, lithium iron phosphate, nickel sulfide, copper sulfide, lithium sulfide, iron oxide, and/or vanadium oxide.
  • LCO lithium cobalt oxide
  • NCA lithium nickel cobalt aluminum oxide
  • NCM lithium nickel cobalt manganese oxide
  • the positive active material of embodiments is not limited thereto and may be any suitable material generally available as a positive active material in the art may also be used.
  • the positive active materials may be used alone or in combination of at least two thereof.
  • the lithium transition metal oxide may be, for example, one selected from the compounds represented by the following formulae: Li a A 1-b B b D 2 (where 0.90 ⁇ a ⁇ 1 and 0 ⁇ b ⁇ 0.5); Li a E 1-b B b O 2-c D c (where 0.90 ⁇ a ⁇ 1, 0 ⁇ b ⁇ 0.5, and 0 ⁇ c ⁇ 0.05); LiE 2-b BbO 4-c D c (where 0 ⁇ b ⁇ 0.5 and 0 ⁇ c ⁇ 0.05); Li a Ni 1-b-c Co b B c D ⁇ (where 0.90 ⁇ a ⁇ 1, 0 ⁇ b ⁇ 0.5, 0 ⁇ c ⁇ 0.05, and 0 ⁇ 2); Li a Ni 1-b-c Co b BcO 2- ⁇ F ⁇ (where 0.90 ⁇ a ⁇ 1, 0 ⁇ b ⁇ 0.5, 0 ⁇ c ⁇ 0.05, and 0 ⁇ 2); Li a Ni 1-b-c Co b B c O 2- ⁇ F 2 (where 0.90 ⁇ a ⁇ 1, 0 ⁇ b ⁇ 0.5, 0 ⁇ c ⁇ 0.05, and 0
  • A is Ni, Co, Mn, or any combination thereof
  • B is Al, Ni, Co, Mn, Cr, Fe, Mg, Sr, V, a rear earth element, or any combination thereof
  • D is O, F, S, P, or any combination thereof
  • E is Co, Mn, or any combination thereof
  • F is F, S, P, or any combination thereof
  • G is Al, Cr, Mn, Fe, Mg, La, Ce, Sr, V, or any combination thereof
  • Q is Ti, Mo, Mn, or any combination thereof
  • I is Cr, V, Fe, Sc, Y, or any combination thereof
  • J is V, Cr, Mn, Co, Ni, Cu, or any combination thereof.
  • the above-described compound having a coating layer formed on the surface thereof, or a mixture of the above-described compound and a compound having a coating layer may be used.
  • the coating layer added to the surface of the above-described compound may include a compound of a coating element such as an oxide, hydroxide, oxyhydroxide, oxycarbonate, and/or hydroxycarbonate of the coating element.
  • the compound constituting the coating layer may be amorphous or crystalline.
  • the coating element included in the coating layer may be Mg, Al, Co, K, Na, Ca, Si, Ti, V, Sn, Ge, Ga, B, As, Zr, or any mixture thereof.
  • the coating layer may be formed by using any suitable method which does not (or substantially does not) adversely affect physical properties of the cathode active material.
  • spray coating and/or immersing may be used.
  • the coating method may be any suitable coating method generally used in the art, and thus, further description thereof is not necessary here.
  • the positive active material includes, for example, a lithium salt of a transition metal oxide having a layered rock salt type structure (e.g., a layered rock salt kind of structure) among the above-described lithium transition metal oxides.
  • a layered rock salt structure is a structure in which a layer of oxygen atoms and a layer of metal atoms are alternately arranged regularly in a ⁇ 111> direction (e.g., a (111) crystal plane) of a cubic rock salt type structure (e.g., a cubic rock salt kind of structure) such that each atomic layer forms a two-dimensional plane.
  • the aforementioned "cubic rock salt type structure” refers to a sodium chloride (NaCI) type or kind of structure, as one of the crystal structures, which may be, for example, a structure in which face centered cubic lattices (FCCs) respectively formed of cations and anions are misarranged (e.g., shifted) by one half the ridge of each unit lattice.
  • NaCI sodium chloride
  • FCCs face centered cubic lattices
  • NCA LiNi x Co y Al z O 2
  • NCM LiNi x Co y Mn z O 2
  • the all-solid secondary battery 1 has increased energy density and/or improved thermal stability.
  • the positive active material may be covered by a coating layer as described above.
  • the coating layer may be any suitable coating layer generally used in the art as a coating layer of a positive active material of all-solid secondary batteries.
  • the coating layer may include, for example, Li 2 O-ZrO 2 (LZO).
  • the positive active material includes nickel (Ni) as a ternary lithium transition metal oxide such as NCA or NCM
  • Ni nickel
  • elution of metal of the positive active material may be reduced during charging by increasing capacity density of the all-solid secondary battery 1.
  • cycle characteristics of the all-solid secondary battery 1 may be improved during charging.
  • the positive active material may have, for example, a particulate shape such as a spherical shape or an oval shape.
  • a particle diameter of the positive active material is not particularly limited in embodiments but may be within any suitable range applicable to positive active materials of existing all-solid secondary batteries.
  • An amount of the positive active material of the positive electrode 10 is not particularly limited in embodiments but may be within any suitable range applicable to positive electrodes of all-solid secondary batteries.
  • the positive active material layer 12 may include, for example, a solid electrolyte.
  • the solid electrolyte included in the positive electrode layer 10 may be the same as or different from a solid electrolyte included in the solid electrolyte layer 30.
  • the solid electrolyte and the solid electrolyte layer 30 are further described elsewhere herein.
  • the solid electrolyte included in the positive active material layer 12 may have a smaller average particle diameter D50 than that of the solid electrolyte included in the solid electrolyte layer 30.
  • the average particle diameter D50 of the solid electrolyte included in the positive active material layer 12 may be 90% or less, 80% or less, 70% or less, 60% or less, 50% or less, 40% or less, 30% or less, or 20% or less of the average particle diameter D50 of the solid electrolyte included in the solid electrolyte layer 30.
  • the positive active material layer 12 may include a binder.
  • the binder may include, for example, styrene butadiene rubber (SBR), polytetrafluoroethylene, polyvinylidene fluoride, and/or polyethylene.
  • the positive active material layer 12 may include a conductive material.
  • the conductive material may include graphite, carbon black, acetylene black, Ketjen black, carbon fiber, and/or metal powder.
  • the positive electrode layer 10 may further include, for example, a filler, a coating agent, a dispersant, and/or an ion-conductive adjuvant, in addition to the positive active material, the solid electrolyte, the binder, and the conductive material as described above.
  • any suitable materials generally used in electrodes of all-solid secondary batteries may be used.
  • Solid Electrolyte Layer Sulfide-based Solid Electrolyte
  • the solid electrolyte layer 30 includes a sulfide based solid electrolyte interposed between the positive electrode 10 and the negative electrode layer 20.
  • the sulfide-based solid electrolyte includes at least one selected from compounds represented by the following formulae: Li 2 S-P 2 S 5 , Li 2 S-P 2 S 5 -LiX (where X is a halogen atom), Li 2 S-P 2 S 5 -Li 2 O, Li 2 S-P 2 S 5 -Li 2 O-LiI, Li 2 S-SiS 2 , Li 2 S-SiS 2 -LiI, Li 2 S-SiS 2 -LiBr, Li 2 S-SiS 2 -LiCl, Li 2 S-SiS 2 -B 2 S 3 -LiI, Li 2 S-SiS 2 -P 2 S 5 -LiI, Li 2 S-B 2 S 3 , Li 2 S-P 2 S 5 -Z m S n (where m and n are positive numbers and Z is Ge, Zn, or Ga), Li 2 S-GeS 2 , Li 2 S-Ge
  • the sulfide-based solid electrolyte may be prepared by treating a starting material such as Li 2 S and P 2 S 5 by melt quenching and/or mechanical milling. In addition, after such treatment, heat treatment may be performed.
  • the solid electrolyte may be in an amorphous state, a crystalline state, or a mixed state thereof.
  • the solid electrolyte may be a solid electrolyte including sulfur (S), phosphorus (P), and/or lithium (Li) as components among materials of the above-described sulfide-based solid electrolyte.
  • the solid electrolyte may be a material including Li 2 S-P 2 S 5 .
  • a mixing ratio of Li 2 S and P 2 S 5 may be, for example, in a range from 50:50 to 90:10.
  • the sulfide-based solid electrolyte may be, for example, an argyrodite-type component (e.g., an argyrodite kind of component) including at least on selected from Li 7-x PS 6-x Cl x (where 0 ⁇ x ⁇ 2), Li 7-x PS 6-x Br x (where 0 ⁇ x ⁇ 2), and Li 7-x PS 6-x I x (where 0 ⁇ x ⁇ 2).
  • the sulfide-based solid electrolyte may have a structure or molecular geometry matching that of argyrodite.
  • the sulfide-based solid electrolyte may have an orthorhombic pyramidal structure.
  • the sulfide-based solid electrolyte may be an argyrodite-type including at least one selected from Li 6 PS 5 Cl, Li 6 PS 5 Br, and Li 6 PS 5 I.
  • a density of the argyrodite-type solid electrolyte may be in a range of 1.5 g/cc to 2.0 g/cc. Because the argyrodite-type solid electrolyte has a density of 1.5 g/cc or more, internal resistance of the all-solid secondary battery may be reduced and penetration of the solid electrolyte may be effectively inhibited or reduced.
  • the solid electrolyte may have a modulus of elasticity in a range of 15 GPa to 35 GPa.
  • the solid electrolyte layer 30 may include a binder.
  • the binder included in the solid electrolyte layer 30 may include styrene butadiene rubber (SBR), polytetrafluoroethylene, polyvinylidene fluoride, and polyethylene.
  • SBR styrene butadiene rubber
  • the binder is not limited thereto in embodiments and any suitable compound generally used as a binder in the art may also be used.
  • the binder of the solid electrolyte layer 30 may be the same or different from the binder included in the positive active material layer 12 and the negative active material layer 22.
  • a thickness of the first negative active material layer may be, for example, 50% or less, 40% or less, 30% or less, 20% or less, 10% or less, or 5% or less of a thickness of the positive active material layer.
  • the thickness of the first negative active material layer may be, for example, in a range of 1 ⁇ m to 20 ⁇ m, 2 ⁇ m to 10 ⁇ m, or 3 ⁇ m to 7 ⁇ m.
  • energy density of the all-solid secondary battery 1 decreases and internal resistance in the all-solid secondary battery 1 increases by or at the first negative active material layer, making it difficult to improve cycle characteristics of the all-solid secondary battery 1.
  • a charging capacity of the first negative active material layer 22 is, for example, 50% or less, 40% or less, 30% or less, 20% or less, 10% or less, 5% or less, or 2% or less of a charging capacity of the positive active material layer 12.
  • a charging capacity of the first negative active material layer 22 is, for example, in a range of 0.1% to 50%, 0.1% to 40%, 0.1% to 30%, 0.1% to 20%, 0.1% to 10%, 0.1% to 5%, or 0.1% to 2% of the charging capacity of the positive active material layer 12.
  • the first negative active material layer 22 becomes too thin so that lithium dendrites formed between the first negative active material layer 22 and the negative current collector 21 during repeated charging and discharging processes causes damages to the first negative active material layer 22, making it difficult to improve cycle characteristics of the all-solid secondary battery 1.
  • the energy density of the all-solid secondary battery 1 decreases and internal resistance of the all-solid secondary battery 1 increases by the first negative active material layer 22, making it difficult to improve cycle characteristics of the all-solid secondary battery 1.
  • the charging capacity of the positive active material layer 12 is obtained by multiplying a charging capacity density (mAh/g) of the positive active material by a mass of the positive active material of the positive active material layer 12.
  • charging capacity ⁇ mass values for each of the positive active materials are respectively calculated and a sum of the values is regarded as the charging capacity of the positive active material layer 12.
  • the charging capacity of the first negative active material layer 22 is calculated in the same manner.
  • the charging capacity of the first negative active material layer 22 is obtained by multiplying the charging capacity (mAh/g) of the negative active material by a mass of the negative active material of the first negative active material layer 22.
  • charging capacity ⁇ mass values for each of the negative active materials are respectively calculated and a sum of the values is regarded as the charging capacity of the first negative active material layer 22.
  • the charging capacity densities of the positive active material and the negative active material are capacities estimated using an all-solid half-cell to which lithium metal is applied as a counter electrode.
  • the charging capacities of the positive active material layer 12 and the first negative active material layer 22 are also directly measured using the all-solid half-cell.
  • the charging capacity density is calculated by dividing the charging capacity by the mass of each active material.
  • the charging capacities of the positive active material layer 12 and the first negative active material layer 22 may be initial charging capacities measured during charging of a first cycle.
  • the negative current collector 21 is formed of a material, which does not react, e.g., does not form (or substantially does not form) an alloy and/or a compound, with lithium.
  • Examples of the material used to form the negative current collector 10 may include copper (Cu), stainless steel, titanium (Ti), iron (Fe), cobalt (Co), and nickel (Ni), but embodiments are not limited thereto, and any suitable material generally used in the art as an electrode current collector may also be used.
  • a thickness of the negative current collector is, for example, in a range of 1 ⁇ m to 20 ⁇ m, for example, 5 ⁇ m to 15 ⁇ m, or, for example, 7 ⁇ m to 10 ⁇ m.
  • the negative current collector 10 may be formed of an alloy or a coating material of one or more metals selected from the above-mentioned metals.
  • the negative current collector 10 may be formed in a plate or foil shape.
  • the all-solid secondary battery 1 may further include a thin film 24 including an element capable of forming an alloy with lithium and formed on the negative current collector 21.
  • the thin film 24 is interposed between the negative current collector 21 and the first negative active material layer 22.
  • the thin film 24 includes, for example, an element capable of forming an alloy with lithium. Examples of the element capable of forming an alloy with lithium include gold, silver, zinc, tin, indium, silicon, aluminum, and bismuth, but embodiments are not limited thereto, and any suitable element generally used in the art that is capable of forming an alloy with lithium may also be used.
  • the thin film 24 is formed of any one of the metals or an alloy of various suitable types or kinds of metals.
  • a thickness d24 of the thin film 24 is, for example, in a range of 1 nm to 800 nm, 10 nm to 700 nm, 50 nm to 600 nm, or 100 nm to 500 nm.
  • the thickness d24 of the thin film 24 is less than 1 nm, it may be difficult to obtain the function (e.g., desired properties) of the thin film 24.
  • the thin film 24 absorbs lithium, and thus, an amount of lithium precipitates decreases in the negative electrode layer so that the all-solid secondary battery 1 may have decreased energy density and deteriorated or reduced cycle characteristics.
  • the thin film 24 may be formed on the negative current collector 10 by, for example, vacuum deposition, sputtering, and/or plating, but the method of embodiments is not limited thereto and any suitable method of forming the thin film 24 generally used in the art may also be used.
  • the first negative active material layer 22 includes a lithium metal composite including lithium metal and an inorganic negative active material.
  • the all-solid secondary battery 1 may further include a second negative active material layer 23 located between the negative current collector 21 and the first negative active material layer 22 by charging (e.g., as a result of charging).
  • the all-solid secondary battery 1 may include the second negative active material layer 23 alone or may further include a second negative active material layer 23 located between the solid electrolyte layer 30 and the first negative active material layer 22 by charging (e.g., as a result of charging).
  • the second negative active material layer 23 is a metal layer including lithium and/or a lithium alloy.
  • the metal layer includes lithium and/or a lithium alloy.
  • the second negative active material layer 23, as a metal layer including lithium serves as, for example, an Li reservoir.
  • lithium alloy examples include an Li-AI alloy, an Li-Sn alloy, an Li-In alloy, an Li-Ag alloy, an Li-Au alloy, an Li-Zn alloy, an Li-Ge alloy, and/or an Li-Si alloy, but embodiments are not limited thereto, and any suitable lithium alloy generally available in the art may also be used.
  • the second negative active material layer 23 may be formed of any one of the alloy and/or lithium, and/or an alloy of various suitable types or kinds of metals.
  • a thickness d23 of the second negative active material layer 23 may be in a range of, but embodiments are not limited to, 1 ⁇ m to 1000 ⁇ m, 1 ⁇ m to 500 ⁇ m, 1 ⁇ m to 200 ⁇ m, 1 ⁇ m to 150 ⁇ m, 1 ⁇ m to 100 ⁇ m, or 1 ⁇ m to 50 ⁇ m.
  • the second negative active material layer 23 may not suitably or appropriately serve as the Li reservoir.
  • mass and volume of the all-solid secondary battery 1 increase and cycle characteristics may deteriorate or be reduced.
  • the second negative active material layer 23 may be, for example, a metal foil having a thickness within any of the ranges described above.
  • the second negative active material layer 23 may be located between the negative current collector 21 and the first negative active material layer 22 before assembling the all-solid secondary battery 1 or precipitated between the negative current collector 21 and the first negative active material layer 22 after assembling the all-solid secondary battery 1.
  • the second negative active material layer 23 When the second negative active material layer 23 is located between the negative current collector 21 and the first negative active material layer 22 before assembling the all-solid secondary battery 1, the second negative active material layer 23, as a metal layer including lithium, serves as an Li reservoir. Cycle characteristics of the all-solid secondary battery 1 including the second negative active material layer 23 may further be improved.
  • an Li foil is located between the negative current collector 21 and the first negative active material layer 22 before assembling the all-solid secondary battery 1.
  • the second negative active material layer 23 is formed by charging after assembling the all-solid secondary battery 1, the second negative active material layer 23 is not included while assembling the all-solid secondary battery 1, and thus, energy density of the all-solid secondary battery 1 increases.
  • the all-solid secondary battery 1 is charged to exceed the charging capacity of the first negative active material layer 22 during charging. That is, in some embodiments, the first negative active material layer 22 is overcharged.
  • lithium is absorbed to the first negative active material layer 22. That is, in some embodiments, the negative active material included in the first negative active material layer 22 forms an alloy or compound with lithium ions migrating from the positive electrode layer 10.
  • the second negative active material layer 23 is a metal layer mainly formed of lithium (e.g., lithium metal).
  • the negative active material included in the first negative active material layer 22 is formed of lithium and a material forming an alloy or compound with lithium.
  • lithium of the first negative active material layer 22 and the second negative active material layer 23, e.g., metal layer is ionized and moves toward the positive electrode layer 10.
  • lithium may be used as a negative active material in the all-solid secondary battery 1.
  • the first negative active material layer 22 covers the second negative active material layer 23, the first negative active material layer 22 serves as a protective layer for the second negative active material layer 23, e.g., the metal layer, and prevents or reduces the growth of lithium dendrites.
  • a short-circuit and a decrease in capacity may be prevented or reduced in the all-solid secondary battery 1, thereby improving cycle characteristics of the all-solid secondary battery 1.
  • the second negative active material layer 23 is formed after assembling the all-solid secondary battery 1, the negative current collector 21, the first negative active material layer 22, and a region therebetween are Li-free regions not including lithium in an early stage or after discharging of the all-solid secondary battery 1.
  • the Li-free regions are regions that are substantially free of lithium (e.g., they only include lithium, if at all, as an incidental impurity) or are completely free of lithium.
  • the method includes: providing a negative electrode layer according to an embodiment; providing a positive electrode layer; preparing a laminated structure by providing a solid electrolyte layer between the negative electrode layer and the positive electrode layer; and pressing the laminated structure.
  • the pressing is performed at a temperature in a range of 25 °C to 90 °C and a pressure of 550 MPa or less, for example, 500 MPa or less, or, for example, 400 MPa to 500 MP, thereby completing preparation of an all-solid secondary battery.
  • Pressing time may vary according to temperature and pressure and may be, for example, less than 30 minutes.
  • the pressing may be performed using, for example, an isostatic press, a roll press, and/or a plate press.
  • An all-solid secondary battery according to an embodiment may be applied to large- and medium-sized batteries and/or energy storage systems (ESS).
  • ESS energy storage systems
  • Zinc (Zn) was coated on a nickel (Ni) current collector having a thickness of 10 ⁇ m, as a negative current collector, to a thickness of 30 nm to form a Zn coating layer and lithium (Li) was plated on the Zn layer to form a Li porous layer.
  • Ni nickel
  • Li lithium
  • a negative electrode layer including a negative current collector and a first negative active material layer located thereon and including LMC was prepared.
  • Negative electrode layers were prepared in substantially the same manner as in Preparation Example 1, except that current collectors and coating layers were formed as shown in Table 1 below respectively and lithium was plated using electrolytic solutions having composition ratios as shown in Table 1 below respectively.
  • a negative electrode layer was prepared in substantially the same manner as in Preparation Example 1, except that a carbon layer was further formed on the first negative active material layer according to a method described below and as shown in Table 2 below, and a Ni current collector having a thickness of 10 ⁇ m was used as a negative current collector.
  • the carbon layer is a layer formed of 93 wt% of carbon black (CB) having a primary particle diameter of about 30 nm and 7 wt% of a polyvinylidene fluoride (PVDF) binder (Kureha Corporation, # 9300) and has a thickness of about 7 ⁇ m after pressing.
  • PVDF polyvinylidene fluoride
  • 0.28 g of the PVDF binder was dissolved in 4 g of N-methylpyrrolidone (NMP) and mixed with 3.72 g of the CB to prepare a slurry.
  • the prepared slurry was coated on a Ni sheet using a bar coater and dried in air at 80 °C for 10 minutes.
  • a laminated structure obtained as described above was dried under vacuum at 40 °C for 10 hours.
  • the dried laminated structure was roll-pressed at a pressure of 300 MPa for 10 minutes to transfer the carbon layer to the first negative active material layer.
  • a negative electrode layer in which the carbon layer was formed on the first negative active material (LMC) layer was prepared.
  • Li was deposited on a Ni current collector by using Li tablets (Japan, HJ Metal) at 250 °C to form a negative electrode layer (deposited lithium negative electrode layer) having a thickness of about 10 ⁇ m.
  • a solid phase Li was extruded on a Ni current collector by an Li cylinder under high pressure conditions (700 ton) to prepare a negative electrode layer having a thickness of about 100 ⁇ m.
  • Negative electrode layers according to Comparative Preparation Examples 4 and 5 were prepared according to the following process under the conditions shown in Table 2 below.
  • Comparative Preparation Example 4 Composite Material Including Ni/lithium Alloy Powder (LiAl) and Inorganic Compound (Lithium Iodide (Lil)))
  • a negative electrode layer was prepared by locating a composite material obtained according to the following process on a Ni current collector having a thickness of 10 ⁇ m as a negative current collector.
  • Powder of a lithium alloy was mixed with lithium iodide (Lil), as an inorganic compound, to a volume ratio of 9:1, and the mixture was heat-treated at about 400 °C and cooled to prepare a composite material including lithium alloy powder (LiAl) and lithium iodide (Lil) as an inorganic compound.
  • a carbon layer was coated on a negative current collector (Ni) to prepare a negative electrode layer.
  • the coating of the carbon layer was performed in substantially the same manner as in Preparation Example 8.
  • the carbon layer was formed in substantially the same manner as in Preparation Example 8.
  • a negative electrode layer formed of a negative current collector alone was prepared.
  • Table 1 Example Process Substrate Electrolytic Solution Li Formation Current Collector Coating Layer Concentration Salt Solvent Amount of DME (vol. %) Name of HFE Amount of HFE (vol. %) Preparation Example 1 Plating Ni Zn 1 M LiFSI 20 HFE-458 80 Preparation Example 2 Ni Zn 1 M 50 50 Preparation Example 3 Ni Zn 1 M 70 30 Preparation Example 4 Ni Zn 1 M 90 10 Preparation Example 5 Ni - 5 M 100 0 Preparation Example 6 Ni Zn 1 M 100 HFE-6512 80 Preparation Example 7 Ni Zn 1 M 20 HFE-347 80 Comparative Preparation Example 1 Deposition Ni - Comparative Preparation Example 2 Rolling Ni Comparative Preparation Example 3 Extrusion Ni Table 2 Example Current Collector Coating Layer First Negative Active Material Layer Carbon Layer (Protective Layer) Preparation Example 8 Ni Zn LMC 7 ⁇ m Comparative Preparation Example 4 Ni None None None Comparative Preparation Example 5
  • the negative electrode layer of Preparation Example 1 was used.
  • a process of preparing a solid electrolyte layer is as described below.
  • poly(styrene-co-butyl acrylate) as an acrylic binder
  • anhydrous octyl acetate was mixed in a Thinky mixer at 1300 rpm for 5 minutes to prepare a positive active material slurry.
  • the slurry was applied to a nonwoven fabric (thickness: 15 ⁇ m or less) on a release polyethylene terephthalate (PET; thickness: 75 ⁇ m or less) using a Bar coater to form a film, liquid components were removed in a convection oven (80 °C, 10 min), and the resultant was dried in a vacuum oven (40 °C, 10 hr) to prepare a solid electrolyte layer (having a thickness of 90 ⁇ m or less before pressing and 45 ⁇ m or less after WIP pressing).
  • PET release polyethylene terephthalate
  • the positive electrode layer was prepared according to the following process.
  • Li 2 O-ZrO 2 -coated active material LiNi 0.6 Co 0.2 Mn 0.2 (NCM)
  • a conductive material carbon nanofiber and carbon black
  • PTFE polytetrafluoroethylene
  • the vacuum-dried positive electrode layer was laminated on a carbon-coated Al current collector and pressed using a roll press to prepare a positive electrode layer.
  • the negative electrode layer was prepared by Li plating and roll-pressing
  • the solid electrolyte layer was prepared by wet-coating the slurry on the nonwoven fabric
  • the positive electrode layer was prepared by kneading and rolling the materials and roll-pressing the resultant.
  • the negative electrode layer, the solid electrolyte layer, and the positive electrode layer were sequentially laminated and the laminated structure was vacuum-packed in a pouch and pressed using a warm isostatic press (WIP) at a pressure of 400 MPa to 550 MPa to prepare a unit cell having a negative electrode layer/solid electrolyte layer/positive electrode layer structure.
  • WIP warm isostatic press
  • Unit cells having a negative electrode layer/solid electrolyte layer/positive electrode layer structure were prepared in substantially the same manner as in Example 1, except that the negative electrode layers according to Preparation Examples 2 to 8 were respectively used instead of the negative electrode layer of Preparation Example 1.
  • a unit cell having a negative electrode layer/solid electrolyte layer/positive electrode layer structure was prepared in substantially the same manner as in Example 1, except that the negative electrode layer according to Comparative Preparation Example 1 was used instead of the negative electrode layer of Preparation Example 1.
  • the negative electrode layer of Comparative Example 1 could not be applied to an all-solid secondary battery including a sulfide-based solid electrolyte to which high temperature and high pressure are applied due to the softness of the lithium metal.
  • Unit cells having a negative electrode layer/solid electrolyte layer/positive electrode layer structure were prepared in substantially the same manner as in Example 1, except that the negative electrode layers of Comparative Preparation Examples 2 to 7 were respectively used instead of the negative electrode layer of Preparation Example 1.
  • the negative electrode layer obtained according to Preparation Example 1 was analyzed using a scanning electron microscope (SEM) and a transmission electron microscope (TEM).
  • SEM scanning electron microscope
  • TEM transmission electron microscope
  • a SU 8030 manufactured by Hitachi
  • FIB-Helios 450F1 Helios 450F1 manufactured by FEI company
  • Cross-sections of samples were pretreated by milling using a Cooling Cross Section Polisher (IB-19520CCP, JOEL) at 6 kV and 320 ⁇ A for 1 hour.
  • the TEM analysis was performed at 3 keV and 0.8 nA.
  • FIG. 2 is an SEM image showing a surface of lithium plated according to Preparation Example 1. Referring thereto, the surface has a structure in which thin lithium strings are loosely entangled.
  • FIG. 3 is a TEM image showing a surface and a cross-section of an LMC layer after pressing.
  • the LMC layer had a thickness of about 30 ⁇ m before pressing, and the thickness of the LMC layer was controlled to about 6.5 ⁇ m after pressing. After pressing, the surface of the LMC layer was very smooth.
  • a surface roughness Rmax of the LMC layer after pressing was measured using an atomic force microscope (AFM).
  • a surface roughness of the LMC layer was also measured.
  • FIG. 4 is a TEM image of a cross-section of an LMC layer after pressing. Referring to the cross-section of the LMC layer, a number of pores and micro-channels each having a size of 0.1 ⁇ m to 1 ⁇ m were observed. Such pores and micro-channels are caused by porosity of the LMC layer, and the surfaces of lithium strings are coated with an SEI formed of lithium fluoride and having a nanometer-scale thickness, thereby forming a composite product in which lithium metal is complexed with lithium fluoride. Because the LMC has a structure in which lithium is surrounded by hard lithium fluoride, elution or liquefaction of lithium caused by high pressure does not occur (or substantially does not occur).
  • Thicknesses of the LMC layers of Preparation Examples 1 to 8 and the negative electrode layers obtained according to Comparative Preparation Examples 1 to 3 were examined.
  • a film thickness of 5 ⁇ m is evaluated as excellent thin film formation (O)
  • a film thickness of 15 ⁇ m is evaluated as poor thin film formation ( ⁇ )
  • a film thickness of 20 ⁇ m is evaluated as impossible to form thin film (X).
  • Thickness deviations of the respective LMC layers of Preparation Examples 1 to 8 and the respective negative electrode layers obtained according to Comparative Preparation Examples 1 to 3 were examined. A thickness deviation of 5% or less is evaluated as excellent (O) and a thickness deviation of 10% or less is evaluated as poor (X).
  • the negative electrode layers according to Preparation Examples 1 to 8 are formed as thin films, have uniformity, and are available under high-pressure conditions, when compared with those of Comparative Preparation Examples 1 to 3.
  • the above-described results were obtained because the negative electrode layers according to Preparation Examples 1 to 8 have a high Young's modulus by including the LMC layer, thereby inhibiting or reducing microshort-circuits during pressing, but microshort-circuits occurred while pressing the negative electrode layers according to Comparative Preparation Examples 1 to 3.
  • XPS analyses of the negative electrode layers obtained according to Preparation Example 1 and Comparative Preparation Example 1 were performed. XPS analyses were performed using a K-alpha X-ray photoelectron spectrometer manufactured by Thermo Scientific.
  • XPS analyses results are shown in FIG. 5 .
  • 0s indicates a case where the LMC layer was etched for 0 second
  • 240s indicates a case where the LMC layer was etched for 240 hours
  • 600s indicates a case where the LMC layer was etched for 600 hours.
  • LiF which was not observed in the deposited Li obtained according to Comparative Preparation Example 1, was observed.
  • LiF was observed in the LMC layer of Preparation Example 1, but was not observed in the deposited Li of Comparative Example 1.
  • C-F and LiF were observed in an AS-is layer (the unetched layer), only LiF was observed therein in FIG. 5 .
  • the LMC layer of Preparation Example 1 has a lower Li content than that of the deposited Li according to Comparative Preparation Example 1 by about 3 at% but includes 2.2 at% of F.
  • the Li content of the LMC layer is lower than that of the deposited Li of Comparative Preparation Example 1 having the same thickness by about 5 to 10 at%
  • Young's moduli of the negative electrode layers obtained according to Preparation Example 1 and Comparative Preparation Example 1 were also measured.
  • the Young's modulus of each negative electrode layer was measured using a DMA Q800 (manufactured by TA Instruments), and the specimen of the negative electrode layer was prepared according to ASTM standard D412 (Type V specimens).
  • the Young's modulus may also be referred to as tensile modulus.
  • FIG. 6 shows moduli of elasticity of the LMC layer of Preparation Example 1 and the deposited lithium layer of Comparative Preparation Example 1 with respect to depth of the layers.
  • LMC layer indicates the result of the LMC layer
  • Evaporated Li indicates the result of the deposited lithium layer.
  • the modulus of elasticity of the LMC layer is about two times higher than that of deposited Li.
  • the modulus of elasticity is an average value of 3 x 3 points at an interval of 50 ⁇ m using a commercially available Micro-indenter (iMicro, Nanomechanics, Inc.). Because highly elastic LiF is included in a composite form, the LMC layer has a high modulus of elasticity.
  • the deposited Li layer of Comparative Preparation Example 1 is suitable as a candidate for the Li reservoir in terms of the Li content and thin film formation in the same thickness.
  • the modulus of elasticity and hardness of the Li reservoir needs to be considered, and thus Young's modulus characteristics are important.
  • the LMC layer of Preparation Example 1 has far better Young's modulus characteristics than those of the deposited Li layer of Comparative Preparation Example 1, and thus the LMC layer is suitable as the negative electrode layer of the sulfide-based all-solid secondary battery.
  • Hardness of the LMC layer of Preparation Example 1 and the deposited lithium layer of Comparative Preparation Example 1 was examined. Hardness was evaluated using a Micro-indenter (iMicro, Nanomechanics, Inc.).
  • the LMC layer had a far higher surface hardness than that of the deposited Li layer and the inside of the LMC layer had a higher hardness than that of the deposited Li layer. On average, an increase in hardness by about 6 times was confirmed.
  • the hardness of the layer decreases, the Li reservoir may be deformed while pressing the sulfide-based solid electrolyte layer under high-temperature and high-pressure conditions, and lithium may penetrate the solid electrolyte layer to cause problems such as cracks and short-circuits.
  • the LMC layer of Preparation Example 1 the above-described issues may be prevented or reduced in advance.
  • each battery was charged at a constant current of 0.1 C until a voltage reached 4.25 V and charged at a constant voltage until the current reached 0.05 C. The charged cell was rested for about 10 minutes and discharged at a constant current of 0.1 C until the voltage reached 2.5 V.
  • each battery was charged at a constant current of 0.2 C until a voltage reached 4.25 V and charged at a constant voltage until the current reached 0.05 C. The charged cell was rested for about 10 minutes and discharged at a constant current of 0.2 C until the voltage reached 2.5 V.
  • Lifespan evaluation was performed by charging the cell at a constant current of 1 C until the voltage reached 4.25 V and at a constant voltage until the current reached 0.05 C. The charged cell was rested for about 10 minutes and discharged at a constant current of 1 C until the voltage reached 2.5 V, and this cycle was repeated 200 times for evaluation.
  • Capacity retention ratio (CRR) was calculated by Equation 1 below, charge/discharge efficiency was calculated by Equation 2 below, and capacity retention ratio and charge/discharge efficiency characteristics were examined and shown in Table 5 below.
  • Capacity retention ratio Lifespan % discharge capacity of 200 th cycle / discharge capacity of 1 st cycle ⁇ 100
  • Charge / discharge efficiency average discharge voltage of 200 th cycle / average charge voltage of 200 th cycle ⁇ 100
  • Example Charge/discharge efficiency (%) Capacity retention ratio (@50 times)(%)
  • the all-solid secondary battery prepared according to Example 8 had higher charge/discharge efficiency and improved lifespan characteristics when compared with the all-solid secondary battery of Comparative Example 5.
  • each battery was charged at a current of 0.1 C until a voltage reached 4.2 V. The charged cell was rested for about 10 minutes and discharged at a constant current of 0.1 C until the voltage reached 2.5 V.
  • each battery was charged at a current of 0.2 C until the voltage reached 4.2 V. The charged cell was rested for about 10 minutes and discharged at a constant current of 0.2 C until the voltage reached 2.5 V.
  • Lifespan evaluation was performed by charging the cell at a current of 0.33 C until the voltage reached 4.2 V. The charged cell was rested for about 10 minutes and discharged at a constant current of 0.33 C until the voltage reached 2.5 V, and this cycle was repeated 230 times for evaluation.
  • Capacity retention ratios were evaluated and shown in FIG. 10 .
  • the all-solid secondary battery of Example 8 had improved capacity retention ratio compared with the all-solid secondary battery of Comparative Example 5.
  • the all-solid secondary battery of Example 8 includes the negative electrode layer in which a carbon layer is further formed on the first negative active material layer.
  • the carbon layer formed as described above further assisted uniform Li nucleation and uniform growth of Li, thereby further improving capacity retention ratio when compared with a case in which the carbon layer was not formed.
  • the all-solid secondary battery includes the negative active material layer including the lithium metal composite and formed on the negative current collector, thereby preventing or reducing liquefaction of lithium which is caused when lithium metal is applied to the negative electrode layer. Also, by using the negative electrode layer, lithium loss of the negative electrode layer caused in the first charging and lithium loss caused by interfacial side reactions during operation of a battery may be compensated, so that an all-solid secondary battery having high capacity, high voltage, high energy density, and/or improved lifespan characteristics may be prepared.

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EP20206270.9A 2019-11-08 2020-11-06 Couche d'électrode négative pour batterie secondaire tout solide, batterie secondaire toutsolide la comprenant et son procédé de préparation Pending EP3819962A1 (fr)

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JP2023103519A (ja) 2022-01-14 2023-07-27 トヨタ自動車株式会社 負極
JP2023103515A (ja) 2022-01-14 2023-07-27 トヨタ自動車株式会社 負極
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